Process for the manufacture of paints



Patented Sept. 1939 UNITED STATES 1,171,851 raocass roar-ms momma: or

* mmrs Herman B. Kipper, Accord, Macs.

Application November 19. 1936, -8crhlNo.111,679

1 In my application Serial No. 100,818 of September -15, 1936, processing is described for the production of paint films from petroleum oils under atmospheric exposure. The incorporation of ammonium halids or the hydro halids of organic amino or imino compounds, or again the ammonium salts of halogen bearing organic acids or phenols, with the paint materials used for film formation, basically constituted my invention. Although the original petroleum oils used showed some unsaturation, further establishment of unsaturation, artificially, increased their value for film formation when used in conjunction with one or more of the above-mentioned compounds incorporated together with pigments and possibly other oils in the paint. Furthermore, chlorinated, un-

' saturated hydrocarbons or petroleum oils were found as the most valuable for the service in question.

2 I shall not describe the processing used by me for production of unsaturatedip'etroleum hydrocarbons. Such processing is well known to the art. My processing for production of chlorinated unsaturated hydrocarbons I shall, however, briefly 25 describe. Two distinctprocesses were used. By

one chlorination and the production of unsaturation of the hydrocarbons was established in a single step. In the other process two steps were used; I shall describe the latter first.

. 30 The primary step of chlorination was simple,

and is one long known to the art. Chlorine was simply passed through the hydrocarbon or petroleum oil and the hydrochloric acid gas given ofl suitably collected as 35 About two hundred grams were used to three kilograms of oil. The chlorinated oil, after washing with water, and decanting from the latter, was

then pumped through a chrome-nickel-iron alloy tube, six. feet long, one and one-half inches intero nal diameter, at superatmospheric pressure, and

maintained at one hundred to sixhundred degrees centigrade by electric resistance furnaces. The temperature employed depended on the quality of oil used. For instance, for a heavy-chlorinated 5 fuel oil a temperature of about four hundred degrees centigrade was employed. The rate of flow was maintained at from five to ten grams per minute. The reaction tube-was'packed loosely with shredded asbestos, on which was spread finely 50 divided copper chloride. A mixture of finely divided copper chloride, iron and copper oxides or the oxides alone, in about equimolecular proportions, was also used as other copper halids in place of the chloride. A superatmospheric pressure of I about thirty pounds was used and the gas, con-v by absorption in water.-

sisting of about ninety percent of nitrogen and ten percent of oxygen, was passed through the tube simultaneously with the oils and at the rate of one to two liters per minute. The oil was collected-in a cooled steel tube, from which it was drawn off at 5 suitable intervals. A superatmospheric pressure of seventy pounds was also used; the gas then contained about seven percent'of oxygen.

Incarrying out oxidation and chlorination simultaneously, the'chlorine was mixed with oxy- 1o gen and diluted withnitrogen! Otherwise, except that copper chloride was'used exclusively-as the catalytic agent, instead. of the oxides of iron and of copper, the operationalmethods were almost precisely those used for partial oxidation alone.

A steel cylinder of about two cubic feet capacity was used as a reservoir for the oxygen, chlorine, nitrogen gas mixture. As an example of a chlorination-oxidation run the reservoir was filled with about two hundred grams of chlorine and a ten percent oxygen, ninety percent nitrogen mixture to about one hundred and fifty pounds superatmospheric pressure. Using this mixture, or one in which chlorine-and oxygen were in about equimolecular proportions, practically saturated.

chlorinated Y hydrocarbons were secured. The hydrochloric acid gas primarily generated is oxidized to chlorine. On the other hand, if forty to fifty grams of chlorine were used, whereas otherwise the oxygen-nitrogen'gas mixture was that already described, chlorinated unsaturated hydrocarbons were produced. Some cracking also probably occurs as shown by the lower boiling points of a considerable fraction of the finished oil. Cracking occurs when using straight petroleum oils, or saturated hydrocarbons, without chlorination. and the method of partial oxidation as outlined, so that it is reasonable to believethat cracking also occurs in the oxidation-chlorination process described. Hydrochloric acid gas may be 40 used in place of chlorine but the operational efil- .ciency of the apparatus is thereby very materially reduced. Your applicant carried out experimentation with the use of the, above gas in place of chlorine.

iodide gave similar incorporated with the paint after the same is,

otherwise fully prepared. Ihave even used these materials as a separate coating to the paint film after the same has been applied. Again I have precipitated ammonium chloride in the oils by using ammonia and hydrochloric acid gases.

Further, I have used aqueous oil emulsions of ammonium again triethanolamine and linseed oil, as plasticizing or emulsifying agents to aid in the speed of film formation. Such aqueous oil emulsions appear to act as catalytic activators. One of these emulsions was made up from five grams of water, four grams of trihydroxyethyl'amine linoleate and ten grams of linseed oil. About thirty percent of this emulsion on the weight of pigment oil was used.

I have used so-called paint thinners, both light and heavy fuel oils, similar lubricating oils and crude petroleum oil for production of unsaturated hydrocarbons as well as for chlorinated unsaturated hydrocarbons. In the paint vehicles I have also used these fabricated oils singly or in combinations, also coal oils, as a mixture of xylenes, or so called solvent naptha", resins, etc. Such combinations of oils as well as of catalytic materials, of course, might be multiplied ad infinitum and I have stressed only the basic points of my invention. I

Among the pigments employed were ferric oxide, lead carbonate'and titanium oxide. Also other emulsifying agents used. were the ammonium salts of oleic and abietic acids and ethyl and butyi crotonates.

I claim:

. 1. A protective coating composition comprising aint oils of the class consisting of liquid uhsaturated petroleum hydrocarbons, pigments and an ammonium halid as a polymerizing catalyst for drying or polymerizing the paint oils to produce hardened coating films.

2. A protective coating composition comprising paint oils ing paint oils or the class consisting of nium unsaturated petroleum hydrocarbons, linseed oil, paint thinners, pigments and an ammonium halid as a polymerizing catalyst for drying or bons, pigments .to produce hardened coating polymerizing the paint oils to produce hardened coating films. a

4. A protective coating composition comprising paint oils of the class consisting of chlorinated unsaturated liquid petroleum hydrocarand an ammonium halid as a polymerizing catalyst for drying o1 polymerizing the paint oils to produce hardened coating films.

5. A protective coating composition comprising paint 011s of the class consisting oi liquid chlorinated unsaturated petroleum hydrocar-, bons, linseed oil, pigments and an ammonium halid as a polymerizing catalyst for drying or polymerizing the paint oils to produce hardened coating films.

6. A protective coating composition comprising paint oils of the class consisting oi liquid chlorinated unsaturated petroleum hydrocarhalid as a polymerizing catalyst for drying or polymerizing the paint oils to produce hardened coatim films.

fl. A protective coating composition comprising paint oils of the class consisting of liquid unsaturated petroleum hydrocarbons and chlorinated unsaturated petroleum hydrocarbons, pigments and an ammonium halid as a polymerizing catalyst, one to twenty percent of the said catalyst on the weight of pigments used, for drying or polymerizing the paint oils to produce hardened coating films.

8. A protective coating composition comprising paint oils of the class consisting of liquid unsaturated petroleum hydrocarbons and chlorinated unsaturated petroleum hydrocarbons, linseed oil, pigments and an ammonium halld as a polymerizing catalyst, one to twenty percent of the said catalyst on the weight of pigments used, for drying or polymerizing the paint oils films.

9. A protective coating composition comprising paint oils oi the class consisting of liquid unsaturated petroleum hydrocarbons and chlorina'ted unsaturated petroleum hydrocarbons, linseed oil, pigments, paint thinners and an ammonium halid as a polymerizing catalyst, one to twenty percent on the weight of pigments used,

oil, paint thinners, pigments, and an ammonium for drying or polymerizing the paint oils to 'produce hardened coating films.

10. A protective coating composition comprising paint oils of the class consisting of liquid unsaturated petroleum hydrocarbons and chlorinated unsaturated petroleum hydrocarbons, linseed oil, paint thinners, pigments and an ammonium chloride as a weight of pigments izing the paint oils toproduce hardened coating polymerizing catalyst, one to twenty percent o fthe said catalystpon the used, for drying or polymer- 

